CN103140560B - Photocurable composition for transparent adhesive sheet - Google Patents
Photocurable composition for transparent adhesive sheet Download PDFInfo
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- CN103140560B CN103140560B CN201180047770.6A CN201180047770A CN103140560B CN 103140560 B CN103140560 B CN 103140560B CN 201180047770 A CN201180047770 A CN 201180047770A CN 103140560 B CN103140560 B CN 103140560B
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- methyl
- adhesive sheet
- acrylate
- sensitive adhesive
- hydroxyl
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
- C08G18/6208—Hydrogenated polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
Abstract
The purpose of the present invention is to provide a one-liquid photocurable composition for a transparent adhesive sheet that will not corrode a conductive layer of a transparent conductive film even when directly bonded to the conductive layer surface, and that has excellent adhesive layer cohesive force, transparency, punch workability, and graded absorption. The present invention relates to a photocurable composition for a transparent adhesive sheet, said composition comprising: a (meth)acrylic group-containing polyolefin compound (A); a (meth)acrylic acid ester having hydroxyl groups (B); a photopolymerizable monomer (C) other than (meth)acrylic acid ester having hydroxyl groups; and a photopolymerization initiator (D), wherein the (meth)acrylic group-containing polyolefin compound (A) is a compound obtained by reacting polyolefin polyol and a polyfunctional isocyanate compound and reacting a predetermined amount of a compound having (meth)acrylic groups, and a carboxyl group-containing monomer is used in a predetermined amount or less with regard to the photopolymerizable monomer (C) other than (meth)acrylic acid ester having hydroxyl groups.
Description
Technical field
The present invention relates to light solidified transparent pressure-sensitive adhesive sheet composition, be characterised in that light solidified transparent pressure-sensitive adhesive sheet composition to be solidified and the light solidified transparent pressure-sensitive adhesive sheet that obtains is fixing with transparent pressure-sensitive adhesive sheet composition for the nesa coating of the laminating of nesa coating, to solidify with transparent pressure-sensitive adhesive sheet composition the nesa coating obtaining fixing with transparent pressure-sensitive adhesive sheet and be characterised in that nesa coating fixes the duplexer that sticks on the conductive layer surface of nesa coating with transparent pressure-sensitive adhesive sheet by fixing nesa coating.
Background technology
In recent years in the field such as portable phone, game machine, start to load touch panel.Touch panel is for using optics with transparent pressure-sensitive adhesive sheet, top layer to be had to its transparency protected and the display unit class optical component such as the liquid-crystal display duplexer forming of fitting of transparent substrate, glass and protection of the nesa coatings such as ITO (tin indium oxide).
The electrostatic detection that is derived from human body when the touch panel of the resistive film mode that pressure when touch panel mainly contains utilization input detects and utilization input is inputted the touch panel of the capacitance-type (capacitive type) at position.In the touch panel of capacitance-type, the conductive layer surface of nesa coating is fixed in the mode contacting with the adhesive layer surface of adhesive sheet.Therefore, the conductive layer surface of nesa coating contacts with binder layer, has thus the oxidizing reaction that metal occurs due to the sour composition containing in tackiness agent, produces the problem that conducting function reduces.Therefore, require high preventing metal corrosion for nesa coating is fixing with adhesive sheet.
As the adhesive sheet with preventing metal corrosion, the adhesive sheet (for example patent documentation 1) that contains preventing metal corrosion agent is proposed.In addition, propose the nitrogen atom composition by containing specified quantitative with respect to the sour composition of binder layer, thereby reduced the corrosive adhesive sheet (for example patent documentation 2) for nesa coating.
But there is preventing metal corrosion agent variable color and make the problems such as optical characteristics reduction in endurance test in the adhesive sheet that contains preventing metal corrosion agent.In addition, for the adhesive sheet of the nitrogen atom composition that contains specified quantitative, the problem that exists the resistance value that can not fully suppress ITO due to the sour composition containing in binder layer to raise.
On the other hand, in touch panel etc., comprise printing step etc. and have the member of step, such as, in portable phone etc., use the touch panel etc. with the member that has applied frame shape printing.In this purposes, adhesive sheet is required to paste the performance of the performance of stationary member and landfill printing step, requires excellent step tracing ability.When transparent pressure-sensitive adhesive sheet can not absorb this step, produce float (bubble, the space) of transparent pressure-sensitive adhesive sheet in the end periphery of printed layers, likely because this visuality of floating (bubble, space) generation reflection of light loss liquid-crystal display reduces.
In order to obtain excellent step absorptivity, transparent pressure-sensitive adhesive sheet softness and bonding force height are favourable, but consider from the reason of formerly recording, and require not high containing sour composition and cementability.For this requirement, the technical scheme (for example patent documentation 3) that comprises using alkoxyalkyl acrylate as principal monomer, the transparent pressure-sensitive adhesive sheet that can take into account good cementability and preventing metal corrosion is not provided containing vinylformic acid (ester) based polymer of specified molecular weight of sour composition and the binder composition of linking agent is disclosed.
But, in polymkeric substance, add the composition that linking agent forms and have following problems: the stability after single component is insufficient, when coated polymeric, need to carry out solvent cut, and the thick adhesive sheet of therefore making more than 100 μ m is very difficult.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-45315 communique
Patent documentation 2: TOHKEMY 2010-144002 communique
Patent documentation 3: TOHKEMY 2009-079203 communique
Summary of the invention
the problem that invention will solve
The problem to be solved in the present invention is, even if the curing transparent pressure-sensitive adhesive sheet obtaining is provided directly fits and also can not corrode conductive layer, the light solidified transparent pressure-sensitive adhesive sheet composition of force of cohesion, the transparency and the stamping-out excellent in workability of binder layer and the one-pack type of step absorptivity excellence the conductive layer surface of nesa coating.And then provide this transparent pressure-sensitive adhesive sheet.
for the scheme of dealing with problems
The foregoing problems that the inventor etc. exist with light solidified transparent pressure-sensitive adhesive sheet take touch panel has been carried out in depth research as background, found that a kind of light solidified transparent pressure-sensitive adhesive sheet composition, the transparency, binding property, the preventing metal corrosion of nesa coating, the step absorptivity of the light solidified transparent pressure-sensitive adhesive sheet that this light solidified transparent pressure-sensitive adhesive sheet composition is solidified and obtain are good, have completed the present invention based on this discovery; Described light solidified transparent pressure-sensitive adhesive sheet has high molecular with composition compounding and has imported the polyolefin urethane acrylate compound of (methyl) acryl of specified quantitative, has (methyl) acrylate, photopolymerization monomer and the Photoepolymerizationinitiater initiater of hydroxyl, and in photopolymerization monomer, the content of carboxyl group-containing monomer is below specified amount.
The present invention is as shown in following (1)～(7).
(1) a kind of light solidified transparent pressure-sensitive adhesive sheet composition, it is characterized in that, it contains (A) weight-average molecular weight is 10,000～300,000 the polyolefin compound that contains (methyl) acryl, (B) there is (methyl) acrylate of hydroxyl, (C) there is photopolymerization monomer beyond (methyl) acrylate of hydroxyl and (D) Photoepolymerizationinitiater initiater, (A) weight-average molecular weight is that 10,000～300,000 the polyolefin compound that contains (methyl) acryl is for making polyolefin polyhydric alcohol react with polyfunctional isocyanate's compound, then react with the compound that to have with respect to residual hydroxyl or isocyanate group be (methyl) acryl of 50～80 % by mole, thereby carbamate (methyl) acrylic compound obtaining to importing (methyl) acryl in molecule, (C) total amount that has a photopolymerization monomer beyond the carboxyl group-containing monomer containing in the photopolymerization monomer beyond (methyl) acrylate of hydroxyl has hydroxyl (methyl) acrylate with respect to (C) is below 0.1 quality %.
(2) according to the light solidified transparent pressure-sensitive adhesive sheet composition (1) described; it is characterized in that; with respect to the total amount of composition for light solidified transparent pressure-sensitive adhesive sheet, contain (A) weight-average molecular weight and be photopolymerization monomer 20～88 quality % beyond 10,000～300,000 the polyolefin compound that contains (methyl) acryl 10～50 quality %, (methyl) acrylate 1～30 quality % that (B) has hydroxyl, (methyl) acrylate that (C) has hydroxyl and (D) Photoepolymerizationinitiater initiater 0.2～5 quality %.
(3) according to the light solidified transparent pressure-sensitive adhesive sheet composition (1) or (2) described, it is characterized in that, the photopolymerization monomer (C) having beyond (methyl) acrylate of hydroxyl does not comprise carboxyl group-containing monomer.
(4) according to the light solidified transparent pressure-sensitive adhesive sheet composition described in any one in (1)～(3), it is characterized in that, the theoretical second-order transition temperature that is had (methyl) acrylate of hydroxyl and (C) had a polymkeric substance that the photopolymerization monomer beyond (methyl) acrylate of hydroxyl forms by (B) is 0 ℃～50 ℃.
(5) a kind of nesa coating is fixing with transparent pressure-sensitive adhesive sheet composition, it is characterized in that, the light solidified transparent pressure-sensitive adhesive sheet composition described in any one in above-mentioned (1)～(4) is solidified and the light solidified transparent pressure-sensitive adhesive sheet that obtains for the laminating of nesa coating.
(6) nesa coating is fixing is characterized in that with a transparent pressure-sensitive adhesive sheet, and above-mentioned by making (5) described nesa coating is fixing to be solidified to obtain with transparent pressure-sensitive adhesive sheet composition.
(7) duplexer, is characterized in that, forms with the conductive layer surface that transparent pressure-sensitive adhesive sheet sticks on nesa coating by the nesa coating above-mentioned (6) Suo Shu is fixing.
the effect of invention
Light solidified transparent pressure-sensitive adhesive sheet of the present invention with composition owing to containing the polyolefin compound that contains (methyl) acryl of the high molecular of having adjusted (methyl) acryloyl base unit weight in composition; step absorptivity, resistance to excellent moisture permeability; further because the content of the carboxyl in composition is below specified amount; can suppress the corrosion of the conductive layer surface of the nesa coating being caused by sour composition; and then owing to containing (methyl) acrylate with hydroxyl in composition, can obtain high force of cohesion and the adaptation to base material.
Embodiment
The present invention is described in detail below.
(light solidified transparent pressure-sensitive adhesive sheet composition)
Light solidified transparent pressure-sensitive adhesive sheet of the present invention contains photopolymerization monomer beyond (A) weight-average molecular weight is 10,000～300,000 the polyolefin compound that contains (methyl) acryl, (B) has hydroxyl (methyl) acrylate, (methyl) acrylate that (C) has hydroxyl and (D) Photoepolymerizationinitiater initiater with composition.
(polyolefin compound that (A) contains (methyl) acryl)
As the polyolefin compound that contains (methyl) acryl, if there is polyolefin backbone and then imported the polyolefin compound of (methyl) acryl, can use.Operable polyolefin backbone in the polyolefin compound that contains (methyl) acryl as (A), can list the skeletons such as polyethylene, polypropylene, ethylene-propylene copolymer, divinyl, isoprene, hydrogenated butadiene polymer, hydrogenated polyisoprene, cycloolefin.Consider from the viewpoint of photostabilization, the transparency (amorphism), operability (liquid state), be preferably hydrogenated butadiene polymer, hydrogenated polyisoprene skeleton.It should be noted that, (methyl) acryl refers to CH
2=CH-CO-or CH
2=C (CH
3)-CO-.
For the polyolefin compound that contains (methyl) acryl for (A) of the present invention; by making (methyl) acrylate with hydroxyl or isocyanate group carry out urethane reaction, import the polyolefin compound that contains (methyl) acryl that (methyl) acryl obtains in molecule, from the viewpoint of cementability, toughness preferably.The synthetic method of the polyolefin compound that contains (methyl) acryl as (A), can exemplify and react the method for carrying out by the following two-stage.
Two-stage reaction as first case is as described below.First, make to have in a part polyfunctional isocyanate's compound (being sometimes referred to as below " polyfunctional isocyanate's compound ") and the polyolefin polyhydric alcohol of more than two isocyanate group, under ratio at isocyanate group equivalent more than hydroxyl equivalent, react the synthetic carbamate prepolymer with isocyanate group.Now, by adjusting the ratio of the hydroxyl equivalent of polyolefin polyhydric alcohol and the isocyanate group equivalent of polyfunctional isocyanate's compound, can adjust molecular weight.Hydroxyl equivalent is larger with the molecular weight of the urethanes that the ratio of isocyanate group equivalent more greatly, obtained, and hydroxyl equivalent is less with the molecular weight of the ratio of isocyanate group equivalent urethanes less, that obtained.Then; make obtained carbamate prepolymer and react as (methyl) vinylformic acid hydroxyalkyl acrylate, (methyl) acrylate single methanol (residual 1 hydroxyl and make various polyvalent alcohols carry out (methyl) acroleic acid esterification and obtain) that is derived from various polyvalent alcohols of (methyl) acrylate with hydroxyl; residual isocyanate group is converted to (methyl) acryl, obtains thus the polyolefin compound that (A) contains (methyl) acryl.As the object lesson of (methyl) vinylformic acid hydroxyalkyl acrylate, can exemplify (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 1,3-butanediol ester, (methyl) vinylformic acid 1,4-butanediol ester, (methyl) vinylformic acid 1,6-hexylene glycol ester, (methyl) acrylate 3-methyl pentanediol etc., can be separately with or combine two or more use.Wherein, from the viewpoint of with reactivity, the light solidified of isocyanate group, be preferably vinylformic acid 2-hydroxy methacrylate.Now, by making alkyl alcohol and isocyanic ester radical reaction, can adjust (methyl) acryl content.Be not particularly limited as operable saturated alcohol, can use the alkyl alcohol of one kind or two or more straight chain type, branched chain type, alicyclic ring type.
Two-stage reaction as second case is as described below.First, polyolefin polyhydric alcohol is reacted under the ratio more than isocyanate group equivalent at hydroxyl equivalent with polyfunctional isocyanate's compound, the urethanes with hydroxyl that synthetic chain length has extended.Now, by adjusting the ratio of the hydroxyl equivalent of polyolefin polyhydric alcohol and the isocyanate group equivalent of polyfunctional isocyanate's compound, can adjust molecular weight.Hydroxyl equivalent is less with the molecular weight of the urethanes that the ratio of isocyanate group equivalent more greatly, obtained, and hydroxyl equivalent is larger with the molecular weight of the ratio of isocyanate group equivalent urethanes less, that obtained.Then,, by making obtained urethanes and (methyl) acrylate reactions that contains isocyanate group, obtain the polyolefin compound that (A) contains (methyl) acryl.Now, by adjusting and the amount of (methyl) acrylate that contains isocyanate group of residual hydroxyl reaction, can adjust the content of (methyl) acryl.(methyl) acrylate that contains isocyanate group can use commercially available compound, or make (methyl) vinylformic acid hydroxyalkyl acrylate, (methyl) acrylate single methanol of being derived from various polyvalent alcohols is reacted with diisocyanate cpd and a synthetic side end has isocyanate group, opposite side end and have (methyl) acrylate that contains isocyanate group of (methyl) acryl.As (methyl) acrylate that contains isocyanate group, can list for example 2-isocyanic ester ethyl (methyl) acrylate, 1, two (acryloyl-oxy ylmethyl) ethyl isocyanates of 1-etc.Wherein, from the viewpoint of with reactivity and the light solidified of hydroxyl, be preferably 2-isocyanic ester ethyl propylene acid esters.
The two-stage reaction of above-mentioned two examples is reacting of hydroxyl and isocyanate group, under for isocyanate group, inactive organic solvent exists, use dibutyl tin laurate, these common urethane catalyzer of dibutyl tin diethyl hexaoate, conventionally at 30～100 ℃, carry out continuously about 1～5 hour.The consumption of urethane catalyzer is generally 50～500ppm by the total mass benchmark of the raw material for reaction.
As the polyfunctional isocyanate's compound using in the present invention, can list the diisocyanate cpds such as such as tolylene diisocyanate, eylylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl-eylylene diisocyanate, isophorone diisocyanate and their hydride.Wherein, consider from the viewpoint of photostabilization, the reactive easiness of controlling, be preferably isophorone diisocyanate.In these a part, have the compound of more than two isocyanate group can be separately with or two or more combination use.Consumption when reacting under the ratio more than hydroxyl equivalent at isocyanate group equivalent, polyfunctional isocyanate's compound, is preferably 1.8～2.2 moles with respect to 1 mole of polyolefin polyhydric alcohol, more preferably 1.9～2.1 moles.More preferably 1.95～2.05 moles.If the consumption of polyfunctional isocyanate's compound is less than 1.8 moles; too high being difficult to of molecular weight of the polyolefin compound that contains (methyl) acryl due to obtained (A) processes; if the consumption of polyfunctional isocyanate's compound more than 2.2 moles, exists the molecular weight of the polyolefin compound that contains (methyl) acryl due to obtained (A) too low and can not fully obtain the tendency of adhesive sheet intensity.Consumption when reacting under the ratio more than isocyanate group equivalent at hydroxyl equivalent, polyfunctional isocyanate's compound, is preferably 0.4～0.6 mole with respect to 1 mole of polyolefin polyhydric alcohol, more preferably 0.45～0.55 mole.More preferably 0.48～0.52 mole.If the consumption of polyfunctional isocyanate's compound is less than 0.4 mole; the molecular weight that has a polyolefin compound that contains (methyl) acryl due to obtained (A) is too low and can not fully obtain the tendency of adhesive sheet intensity; if the consumption of polyfunctional isocyanate's compound is more than 0.6 mole, too high being difficult to of molecular weight of the polyolefin compound that contains (methyl) acryl due to obtained (A) processes.
It is carbamate (methyl) acrylic compound of 10,000～300,000 the polyolefin compound that contains (methyl) acryl as (A) of the present invention weight-average molecular weight; by polyolefin polyhydric alcohol is reacted with polyfunctional isocyanate's compound, polymer quantizes, and then importing is (methyl) acryl of 50～80 % by mole with respect to residual hydroxyl or isocyanate group.More preferably importing with respect to residual hydroxyl or isocyanate group is (methyl) acryl of 55～75 % by mole, further preferably imports (methyl) acryl of 60～70 % by mole.When the ratio of importing (methyl) acryl is less than 50 % by mole, existence can not import the polyolefin polyhydric alcohol of (methyl) acryl, and bounding force likely reduces, so not preferred.While importing the ratio of (methyl) acryl more than 80 % by mole, it is really up to the mark that the adhesive sheet obtaining likely becomes, so not preferred.
(A) the molecular weight preferable weight-average molecular weight that contains the polyolefin compound of (methyl) acryl is 10,000～300,000, more preferably 20,000～200,000, more preferably 50,000～100,000.The adjustment of molecular weight can be undertaken by the amount of adjusting polyolefin polyhydric alcohol and polyfunctional isocyanate's compound.Weight-average molecular weight less than 10,000 o'clock, because the force of cohesion of obtained adhesive sheet reduces, the intensity of adhesive sheet is likely insufficient, so not preferred.In addition, molecular weight is greater than at 300,000 o'clock, and because light solidified transparent pressure-sensitive adhesive sheet was processed with too high being difficult to of viscosity of composition, the remarkable variation of operability, so not preferred.It should be noted that, the value of the weight-average molecular weight in the present invention is for being used gel permeation chromatography (the Shodex GPC-101 processed of Showa Denko K. K), and normal temperature is measured under the following conditions, the value of utilizing polystyrene conversion to try to achieve.
Chromatographic column: clear and electrician LF-804 processed
Column temperature: 40 ℃
Sample: 0.2 quality % tetrahydrofuran solution of multipolymer
Flow: 1ml/ minute
Elutriant: tetrahydrofuran (THF)
The content of the polyolefin compound that contains (methyl) acryl as (A), at light solidified transparent pressure-sensitive adhesive sheet with being preferably 10～50 quality % in composition, more preferably 15～45 quality %, more preferably 20～40 quality %.While being less than 10 quality %, the adhesive sheet obtaining becomes fragile, so not preferred.During more than 50 quality %, the bounding force of the adhesive sheet obtaining likely reduces, so not preferred.
((B) has hydroxyl (methyl) acrylate)
(methyl) acrylate as (B) with hydroxyl does not preferably have carboxyl, (methyl) vinylformic acid hydroxyalkyl acrylate that the carbonatoms that can list such as alkyl is 2～7 etc., as their concrete example, can exemplify (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 1, 3-butanediol ester, (methyl) vinylformic acid 1, 4-butanediol ester, (methyl) vinylformic acid 1, 6-hexylene glycol ester, (methyl) vinylformic acid 3-methyl pentanediol ester etc., can be separately with or two or more combination use.Wherein, consider from the viewpoint of the bounding force of obtained adhesive sheet, be preferably vinylformic acid 2-hydroxy methacrylate.There is the content of (methyl) acrylate of hydroxyl as (B), preferably at light solidified transparent pressure-sensitive adhesive sheet with containing 1～30 quality % in composition, more preferably 5～25 quality %, more preferably 10～20 quality %.When less than 1 quality %, the adhesive sheet obtaining is insufficient to the adaptation of base material, so not preferred.In addition, during more than 30 quality %, the water tolerance variation of adhesive sheet, so not preferred.
((C) has the photopolymerization monomer beyond hydroxyl (methyl) acrylate)
(C) there is photopolymerization monomer (being sometimes referred to as below " photopolymerization monomer (C) ") beyond (methyl) acrylate of hydroxyl and refer to it for photopolymerization monomer and for the photopolymerization monomer except thering is (methyl) acrylate of hydroxyl, be preferably the monomer that does not contain carboxyl (chemical formula :-COOH).Be not particularly limited as this monomer, can by have the simple function of vinyl, (methyl) acryl etc. or multi-functional photopolymerization monomer separately with or two or more combination use.As the photopolymerization monomer of (C) of the present invention, for example can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) isodecyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, (methyl) alkyl acrylates such as (methyl) tridecyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid norborneol alkyl ester, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid double cyclopentenyl 2-ethoxyethyl acetate, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) vinylformic acid dicyclo amyl group 2-ethoxyethyl acetate, (methyl) vinylformic acid cyclic alkyl esters such as tristane dihydroxymethyl two (methyl) acrylate etc.Can list (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid butoxyethyl, (methyl) vinylformic acid 2-methoxy ethoxy ethyl ester, (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid 2-ethoxy ethoxy ethyl ester, methoxyl group glycol ether (methyl) acrylate, ethoxydiglycol (methyl) acrylate, alkoxyl group (gathering) aklylene glycol (methyl) acrylate such as methoxyl group dipropylene glycol (methyl) acrylate, (methyl) vinylformic acid fluorinated alkyl esters such as (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, (methyl) propenoic acid dialkyl aminoalkyl esters such as N-diethylamino ethyl ester, polyoxyethylene glycol two (methyl) acrylate, glycol ether two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triglycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, hydroxy new pentane acid ester neopentyl glycol two (methyl) acrylate, two (hydroxyethyl)-5 of 1,3-, 5-T10 two (methyl) acrylate, α, the two glycol ether phthalic esters of ω-bis-(methyl) acryl, trimethylolpropane tris (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, two acryloxy ethyl phosphonic acid esters, Dipentaerythritol trihydroxy-(methyl) acrylate, multi-functional (methyl) acrylate such as tetramethylolmethane four (methyl) acrylate, acrylamide and DMAA, diethyl acrylamide, the acrylamide derivatives such as (methyl) acryloyl morpholine, (methyl) acrylate that (methyl) glycidyl acrylate etc. contains epoxy group(ing) etc.As the photopolymerization monomer of (C) of the present invention; consider from Combination, the binding property of adhesive sheet, intensity, photostabilization, the stable on heating viewpoint of the polyolefin compound that contains (methyl) acryl with (A), be preferably (methyl) alkyl acrylate or (methyl) vinylformic acid cyclic alkyl ester.Refer to (methyl) acryl at this alleged simple function or polyfunctional functional group.(C) content of photopolymerization monomer preferably at light solidified transparent pressure-sensitive adhesive sheet with containing 20～88 quality % in composition, more preferably 20～70 quality %.More preferably 40～69 quality %.When less than 20 quality %, the adhesive sheet obtaining is insufficient to the adaptation of base material, so not preferred.In addition, during more than 88 quality %, because the force of cohesion of adhesive sheet reduces, bounding force reduces, so not preferred.
In the present invention, for the carboxyl group-containing monomer such as vinylformic acid, methacrylic acid containing in the photopolymerization monomer of (C), be below 0.1 quality % with respect to the total amount of the photopolymerization monomer of (C), more preferably below 0.05 quality %.(C) photopolymerization monomer does not further preferably comprise carboxyl group-containing monomer.If carboxyl group-containing monomer exceedes 0.1 quality % with respect to the total amount of the photopolymerization monomer of (C) and is difficult to the corrosion of the conductive layer surface that suppresses nesa coating.
The theoretical second-order transition temperature that has the polymkeric substance that (methyl) acrylate of hydroxyl and photopolymerization monomer (C) form by (B) of the present invention is from the intensity of adhesive sheet, the viewpoint consideration of bonding force, be preferably 0～50 ℃, more preferably 5～45 ℃, more preferably 10～40 ℃.During lower than 0 ℃, the adhesive sheet obtaining is because the impact of the polyolefin compound that (A) contains (methyl) acryl becomes too soft, and therefore the bonding force of adhesive sheet reduces, so not preferred.In addition, during higher than 50 ℃, the adhesive sheet obtaining is really up to the mark, can not get sufficient binding property, so not preferred.At this, theoretical second-order transition temperature (Tg) can be calculated by the formula (1) of following FOX by the Tg of homopolymer (homopolymer) and the massfraction of this monomer (copolymerization ratio) of each monomer based on forming raw material monomer.
[mathematical expression 1]
1/Tg=W
1/T
1+W
2/T
2+…W
n/T
n (1)
W in formula (1)
1, W
2w
nfor the massfraction (=(compounding amount/monomer total mass of each monomer)) of each monomer, T
1, T
2t
nfor the second-order transition temperature (absolute temperature) of the homopolymer of each monomer.As the Tg of homopolymer, adopt the value of recording as in " Nian Ji Intraoperative Ha Application De Block ッ Network " (" adhering technique handbook ") of the Nikkan Kogyo Shimbun of Co., Ltd. of known data or " Polymer Handbook " (" polymer handbook ") of Wiley-Interscience.For the Tg of homopolymer of the monomer of not recording in above-mentioned known data, adopt the value of being tried to achieve by following method.That is, the monomer that becomes object is carried out to solution polymerization and obtain homopolymer solution, make this homopolymer solution curtain coating on release liner dry, make test sample.For this test sample, use differential scanning calorimeter (DSC) to make temperature be changed to 280 ℃ from-80 ℃ with the heat-up rate of 10 ℃/min and carry out means of differential scanning calorimetry mensuration, adopt the heat absorption starting temperature of glass transition as the Tg of this homopolymer.
((D) Photoepolymerizationinitiater initiater)
As (D) Photoepolymerizationinitiater initiater in the present invention, can list such as carbonyl and be Photoepolymerizationinitiater initiater, sulfide-based Photoepolymerizationinitiater initiater, quinone is that Photoepolymerizationinitiater initiater, azo are that Photoepolymerizationinitiater initiater, SULPHURYL CHLORIDE are that Photoepolymerizationinitiater initiater, thioxanthone are Photoepolymerizationinitiater initiater, peroxidation system Photoepolymerizationinitiater initiater etc.
Be Photoepolymerizationinitiater initiater as carbonyl, can list for example benzophenone, dibenzoyl, bitter almond oil camphor, ω-bromoacetophenone, monochloroacetone, methyl phenyl ketone, 2, 2-diethoxy acetophenone, 2, 2-dimethoxy-2-phenyl methyl phenyl ketone, to dimethylamino benzoylformaldoxime, to dimethylamino Propiophenone, 2-chlorobenzophenone, 4, 4 '-dichloro benzophenone, 4, 4 '-bis-diethylamino benzophenone, Michler's keton, benzoin methylether, bitter almond oil camphor ethyl isobutyl ether, benzoin n-butylether, benzil dimethyl ketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, benzoyl methyl-formiate, 2, 2-diethoxy acetophenone, 4-N, N '-dimethyl acetophenone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone etc.
As sulfide-based Photoepolymerizationinitiater initiater, can list such as Diphenyl disulfide ether, benzyldithio toluene, tetraethylthiuram disulfide, tetramethyl-one ammonium sulfide etc.Be Photoepolymerizationinitiater initiater as quinone, can list such as benzoquinones, anthraquinone etc.Be Photoepolymerizationinitiater initiater as azo, can list for example azobis isobutyronitrile, 2,2 '-di-isopropyl diazene (2,2 '-azobispropane), hydrazine etc.Be Photoepolymerizationinitiater initiater as thioxanthone, can list such as thioxanthone, CTX, 2-methyl thioxanthone etc.As peroxidation system Photoepolymerizationinitiater initiater, can list such as benzoyl peroxide, di-t-butyl peroxide etc.In these (D) Photoepolymerizationinitiater initiaters, from considering by the deliquescent viewpoint composition at obtained light solidified transparent pressure-sensitive adhesive sheet, be preferably 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone.These (D) Photoepolymerizationinitiater initiaters can be separately with or two or more combination use.
Consider from the viewpoint of the intensity of light solidified and the adhesive sheet that obtains, fusible balance, (D) content of Photoepolymerizationinitiater initiater preferably at light solidified transparent pressure-sensitive adhesive sheet with in composition being 0.2～5 quality %, more preferably 0.5～3 quality %.If there is the inadequate tendency of photocuring in the quantity not sufficient 0.2 quality % that contains of Photoepolymerizationinitiater initiater (D), if exceed the tendency that 5 quality % exist the binding property of obtained adhesive sheet to reduce, so not preferred.
For light solidified transparent pressure-sensitive adhesive sheet of the present invention with for composition, preferably the total amount with composition with respect to light solidified transparent pressure-sensitive adhesive sheet, contains 10～50 quality % (A) compositions, 1～30 quality % (B) composition, 20～88 quality % (C) compositions and 0.2～5 quality % (D) composition.And, more preferably the total amount with composition with respect to light solidified transparent pressure-sensitive adhesive sheet, contains 15～45 quality % (A) compositions, 5～25 quality % (B) compositions, 20～70 quality % (C) compositions and 0.2～5 quality % (D) composition.And, the total amount of further preferably using composition with respect to light solidified transparent pressure-sensitive adhesive sheet, contains 20～40 quality % (A) compositions, 10～20 quality % (B) compositions, 40～69 quality % (C) compositions and 0.5～3 quality % (D) composition.
Light solidified transparent pressure-sensitive adhesive sheet of the present invention is with in composition, in order to improve the bonding force of obtained adhesive sheet, can also be as required can not reducing in transparent scope and add tackifying resin.As the example of tackifying resin, can list the rosin series resins such as the carboxylate of rosin, rosin, the terpenes such as diterpene polymkeric substance, α-pinene-phenol multipolymer are resin, the petroleum resin such as fat family (C5 system), fragrant family (C9 system), and phenylethylene resin series, phenolic aldehyde are resin, xylene resin etc.Consider from sunproof viewpoint, preferably the carboxylate of the carboxylate of staybelite few unsaturated double-bond, nilox resin, aliphatics through-stone oleo-resinous, aromatic series through-stone oleo-resinous, high Tg vinylformic acid (ester) resin etc. are added in adhesive sheet.As the addition of tackifying resin, preferably add 1～10 mass parts with respect to composition 100 mass parts for light solidified transparent pressure-sensitive adhesive sheet (with respect to (A) composition, (B) composition, (C) composition and (D) total amount 100 mass parts of composition).
In addition, light solidified transparent pressure-sensitive adhesive sheet of the present invention is with in composition, as required, can also contain known various additive not damaging in transparent scope.As additive, can list the such static inhibitor of the photostabilizers such as softening agent, surface lubricant, flow agent, tenderizer, antioxidant, protective agent, photostabilizer, UV light absorber, stopper, benzotriazole system, phosphoric acid ester system and other fire retardant, tensio-active agent etc.
In addition, the viscosity while coating in order to adjust, light solidified transparent pressure-sensitive adhesive sheet of the present invention can also with an organic solvent form solution with composition.As used organic solvent, can list such as methylethylketone, acetone, ethyl acetate, tetrahydrofuran (THF), diox, pimelinketone, normal hexane, toluene, dimethylbenzene, n-propyl alcohol, Virahol etc.These organic solvents can use separately or two or more mixing.
(nesa coating is fixing with transparent pressure-sensitive adhesive sheet composition)
Nesa coating of the present invention is fixing with adhesive sheet composition, for the nesa coating that comprises above-mentioned light solidified transparent pressure-sensitive adhesive sheet composition is fixed with adhesive sheet composition.
As using the fixing nesa coating with adhesive sheet composition of nesa coating of the present invention, if at least the top layer of one side has the nesa coating of conductive layer, can list the nesa coating that conducting material is set by evaporation, coating on the top layer of transparent substrate.Evaporation, the conducting material that is coated in the conductive layer of nesa coating are not particularly limited, particularly, can list tin indium oxide, Indium sesquioxide, stannic oxide, zinc oxide, Cadmium oxide, gallium oxide, titanium oxide etc.Wherein, be applicable to using the tin indium oxide of the transparency, excellent electric conductivity.In nesa coating, be not particularly limited as the base material of evaporation, coated with conductive material, can list glass, resin film etc.
(nesa coating is fixing with transparent pressure-sensitive adhesive sheet)
Nesa coating of the present invention is fixing is to make above-mentioned nesa coating fixing fixing with transparent pressure-sensitive adhesive sheet with the curing nesa coating forming of transparent pressure-sensitive adhesive sheet composition with transparent pressure-sensitive adhesive sheet, can paste suitably with the conductive layer surface of nesa coating and be difficult for producing the corrosion of conductive layer.Therefore, nesa coating is fixing pastes with the conductive layer surface of transparent pressure-sensitive adhesive sheet and nesa coating the duplexer forming and can be used as suitably touch panel.In addition, nesa coating of the present invention fixing with transparent pressure-sensitive adhesive sheet can be for thering is the adhesive sheet of base material or not thering is the double-sided adhesive sheet that base material is only formed by binder layer.In addition, binder layer can only be formed by simple layer or stacked multilayer forms.Wherein, consider from the viewpoint of guaranteeing the transparency, product having shape-following-up properties, be preferably the double-sided adhesive sheet that does not there is base material and only formed by binder layer.
Nesa coating of the present invention is fixing can be obtained as follows with transparent pressure-sensitive adhesive sheet: on demoulding PET film, be coated with nesa coating and fix with transparent pressure-sensitive adhesive sheet composition, be coated with composition used to the irradiation ultraviolet radiations such as UV irradiation equipment and make its photocuring, can obtain thus nesa coating of the present invention and fixedly use transparent pressure-sensitive adhesive sheet.Nesa coating is fixing is preferably 5～500 μ m, more preferably 10～300 μ m with the thickness of adhesive sheet.Be thinner than with the thickness of adhesive sheet the laminating that 5 μ m are difficult to carry out adhesive sheet and be thicker than the tendency that 500 μ m are difficult to control thickness if nesa coating is fixing if exist.
Embodiment
With comparative example, the present invention is carried out to more specific description by the following examples, but the present invention is not subject to any restriction of these examples.
Polyolefin compound (A-1) > that < contains (methyl) acryl
Add 2 mole of isophorone diisocyanate and 1 mole of C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system to having in the four neck flasks of cooling tube of thermometer, agitator, dropping funnel, subsidiary drying tube, goods name: GI-3000, hydroxyl value 25mgKOH/g), at 60 ℃, react 4 hours, obtain isocyanate group end hydrogenated butadiene polymer.Add wherein 1.4 mol propylene acid 2-hydroxy methacrylate (being 70 % by mole with respect to residual isocyanate base) and 0.6 mole of isopropylcarbinol; be warming up to 70 ℃ of reactions 2 hours; measure and confirm after isocyanate group disappearance by IR; finish reaction, the polyolefin compound (A-1) (weight-average molecular weight is 50000) that is contained (methyl) acryl.
Polyolefin compound (A-2) > that < contains (methyl) acryl
To thering is thermometer, agitator, dropping funnel, in four neck flasks of the cooling tube of subsidiary drying tube, add 1 mole of isophorone diisocyanate and 2 moles of C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's systems, goods name: GI-3000, hydroxyl value 25mgKOH/g), at 60 ℃, react, be the time point below 0.1% at residual isocyanate base, add 1.4 moles of 2-isocyanic ester ethyl propylene acid esters (being 70 % by mole with respect to residual hydroxyl), be warming up to 70 ℃ of reactions 2 hours, measure and confirm after isocyanate group disappearance by IR, finish reaction, the polyolefin compound (A-2) (weight-average molecular weight is 50000) that is contained (methyl) acryl.
Polyolefin compound (A-3) > that < contains (methyl) acryl
Add 2 mole of isophorone diisocyanate and 1 mole of C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system to having in the four neck flasks of cooling tube of thermometer, agitator, dropping funnel, subsidiary drying tube, goods name: GI-3000, hydroxyl value 25mgKOH/g), at 60 ℃, react 4 hours, obtain isocyanate group end hydrogenated butadiene polymer.Add wherein 2.0 mol propylene acid 2-hydroxy methacrylates (being 100 % by mole with respect to residual isocyanate base); be warming up to 70 ℃ of reactions 2 hours; measure and confirm after isocyanate group disappearance by IR; finish reaction, the polyolefin compound (A-3) (weight-average molecular weight is 50000) that is contained (methyl) acryl.
Polyolefin compound (A-4) > that < contains (methyl) acryl
Add 2 mole of isophorone diisocyanate and 1 mole of C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system to having in the four neck flasks of cooling tube of thermometer, agitator, dropping funnel, subsidiary drying tube, goods name: GI-3000, hydroxyl value 25mgKOH/g), at 60 ℃, react 4 hours, obtain isocyanate group end hydrogenated butadiene polymer.Add wherein 0.4 mol propylene acid 2-hydroxy methacrylate (being 20 % by mole with respect to residual isocyanate base) and 1.6 moles of isopropylcarbinols; be warming up to 70 ℃ of reactions 2 hours; measure and confirm after isocyanate group disappearance by IR; finish reaction, the polyolefin compound (A-4) (weight-average molecular weight is 50000) that is contained (methyl) acryl.
Polyolefin compound (A-5) > that < contains (methyl) acryl
Add 1.4 moles of 2-isocyanic ester ethyl propylene acid esters and 1 mole of C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system to having in the four neck flasks of cooling tube of thermometer, agitator, dropping funnel, subsidiary drying tube; goods name: GI-1000; hydroxyl value 75mgKOH/g); at 60 ℃, react 4 hours; measure and confirm after isocyanate group disappearance by IR; finish reaction, the polyolefin compound (A-5) (weight-average molecular weight is 5000) that is contained (methyl) acryl.
Polyolefin compound (A-6) > that < contains (methyl) acryl
Add 1.5 mole of isophorone diisocyanate and 1 mole of C-terminal hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's system to having in the four neck flasks of cooling tube of thermometer, agitator, dropping funnel, subsidiary drying tube, goods name: GI-3000, hydroxyl value 25mgKOH/g), at 60 ℃, react 4 hours, obtain isocyanate group end hydrogenated butadiene polymer.Add wherein 0.8 mol propylene acid 2-hydroxy methacrylate (being 80 % by mole with respect to residual isocyanate base) and 0.2 mole of isopropylcarbinol, be warming up to 70 ℃ and react, quantize but there is polymer, reaction is gelation midway.
Embodiment 1～6, comparative example 1～4
With the compounding respectively of the composition shown in table 1, under room temperature, use dispersion machine to mix, prepare thus uniform light solidified transparent pressure-sensitive adhesive sheet composition.Use apparatus for coating by prepared light solidified transparent pressure-sensitive adhesive sheet with composition with 200 μ m thickness be coated on demoulding PET film (100mm × 100mm × 100 μ m) on, after upper surface covers with the thick demoulding PET film of 25 μ m, use UV irradiation equipment (Nippon Storage Battery Co., Ltd's system, UV irradiating unit 4kw × 1, output: 160W/cm, metal halide lamp), at irradiation distance 12cm, lamp translational speed 20m/ minute, the about 500mJ/cm of irradiation dose
2condition under irradiation ultraviolet radiation make above-mentioned light solidified transparent pressure-sensitive adhesive sheet composition solidify, the thickness that obtains being clipped by demoulding PET film is the adhesive sheet of approximately 200 μ m.
(reckoning of theoretical second-order transition temperature)
For embodiment and comparative example, the theoretical second-order transition temperature by used (B) with the polymkeric substance that (methyl) acrylate of hydroxyl and photopolymerization monomer (C) form is calculated by above-mentioned formula (1).Result is as shown in table 1.
(resistance value of indium tin oxides film is measured)
To be cut by adhesive sheet obtained above the size of 50mm × 50mm, peel off the demoulding PET film that 25 μ m are thick, fit in 100mm × 100mm evaporation the indium tin oxides film surface of PET film of tin indium oxide.Use resistance value determinator Mitsubishi chemical Co., Ltd's system " Loresta-GP " to measure initial resistance value (R1) to the two ends of fitted adhesive sheet.By be fitted with adhesive sheet evaporation the PET film of tin indium oxide under 60 ℃, 90%RH condition, place 500 hours, under 23 ℃, 50%RH condition, place after 1 hour, measure the resistance value (R with initial same area
2).The resistance value rate of rise of indium tin oxides film is calculated by following formula (2).
[mathematical expression 2]
Resistance value rate of rise (the %)=((R of indium tin oxides film
2-R
1)/R
1) × 100 (2)
The evaluation of resistance value rate of rise is undertaken by following benchmark.Result is as shown in table 1.
Zero: resistance value rate of rise less than 5%
△: resistance value rate of rise is more than 5% and less than 10%
×: resistance value rate of rise is more than 10%
(bounding force of adhesive sheet is measured)
To be cut by adhesive sheet obtained above the size of 25 × 100mm, peel off after the demoulding PET film that in the demoulding PET film that is present in adhesive sheet two sides, 100 μ m are thick, adhesive face (mensuration face) is pasted on test board, make reciprocal 1 time of the rubber rollers (width: about 50mm) of 2kg, make test sample.Use sheet glass as test board.For obtained test sample, under 23 ℃, the environment of humidity 50%, place 24 hours, carry out the tension test of 180 degree directions according to JIS Z0237 with 300mm/ minute peeling rate, measure the bounding force (N/25mm) of adhesive sheet to sheet glass.The measured value obtaining is as bounding force.Result is as shown in table 1.
(total light transmittance mensuration)
To be cut by adhesive sheet obtained above the size of 30mm × 30mm, peel off the thick demoulding PET film of 25 μ m in the demoulding PET film that is present in adhesive sheet two sides, be fitted on sheet glass, using gained duplexer as test sample.Use Murakami K. K.'s dye technology institute system " HR-100 type " for test sample, measure total light transmittance (%).Result is as shown in table 1.
(step absorptivity)
At the PET film of being fitted by adhesive sheet obtained above, (thickness 25 μ m), make the step band of total thickness 225 μ m.The periphery along four limits at rectangular glass sheet interarea is pasted above-mentioned step band with frame shape, makes sheet glass with the level.Paste adhesive sheet for whole for the face that is pasted with step band of this sheet glass with the level, the floating of the bonding coat of visual inspection step part.
The absorbefacient evaluation of step is undertaken by following benchmark.Result is as shown in table 1.
Zero: the state that the bonding coat unconfirmed part with step is floated is as qualified
×: will confirm that the state floating is as defective
[table 1]
As shown in Table 1, the light solidified transparent pressure-sensitive adhesive sheet composition of the present invention obtaining in embodiment compared with comparative example, resistance value rate of rise, total light transmittance, bounding force, step absorptivity excellence.
utilizability in industry
Light solidified transparent pressure-sensitive adhesive sheet of the present invention with composition owing to thering is the high transparency, preventing metal corrosion, step absorptivity, binding property excellence, fixing as nesa coating is useful with adhesive sheet, and being fixedly used for of the nesa coating particularly using in the touch panel for capacitance-type says useful.
Claims (6)
1. a light solidified transparent pressure-sensitive adhesive sheet composition, it is characterized in that, it contains (A) weight-average molecular weight is 10,000～300,000 the polyolefin compound that contains (methyl) acryl, (B) there is (methyl) acrylate of hydroxyl, (C) there is photopolymerization monomer beyond (methyl) acrylate of hydroxyl and (D) Photoepolymerizationinitiater initiater, (A) weight-average molecular weight is that 10,000～300,000 the polyolefin compound that contains (methyl) acryl is for making polyolefin polyhydric alcohol react with polyfunctional isocyanate's compound, then react with the compound that to have with respect to residual hydroxyl or isocyanate group be (methyl) acryl of 50～80 % by mole, thereby carbamate (methyl) acrylic compound obtaining to importing (methyl) acryl in molecule, (C) total amount that has a photopolymerization monomer beyond the carboxyl group-containing monomer containing in the photopolymerization monomer beyond (methyl) acrylate of hydroxyl has hydroxyl (methyl) acrylate with respect to (C) is below 0.1 quality %
With respect to the total amount of composition for light solidified transparent pressure-sensitive adhesive sheet, contain (A) weight-average molecular weight and be photopolymerization monomer 20～88 quality % beyond 10,000～300,000 the polyolefin compound that contains (methyl) acryl 10～50 quality %, (methyl) acrylate 1～30 quality % that (B) has hydroxyl, (methyl) acrylate that (C) has hydroxyl and (D) Photoepolymerizationinitiater initiater 0.2～5 quality %.
2. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1, is characterized in that, the photopolymerization monomer (C) having beyond (methyl) acrylate of hydroxyl does not comprise carboxyl group-containing monomer.
3. light solidified transparent pressure-sensitive adhesive sheet composition according to claim 1, it is characterized in that, the theoretical second-order transition temperature that is had (methyl) acrylate of hydroxyl and (C) had a polymkeric substance that the photopolymerization monomer beyond (methyl) acrylate of hydroxyl forms by (B) is 0 ℃～50 ℃.
4. nesa coating is fixing with a transparent pressure-sensitive adhesive sheet composition, it is characterized in that, makes the laminating of the curing and light solidified transparent pressure-sensitive adhesive sheet that obtains of light solidified transparent pressure-sensitive adhesive sheet composition claimed in claim 1 for nesa coating.
5. nesa coating is fixing is characterized in that with a transparent pressure-sensitive adhesive sheet, and by making, nesa coating claimed in claim 4 is fixing to be solidified to obtain with transparent pressure-sensitive adhesive sheet composition.
6. a duplexer, is characterized in that, forms with the conductive layer surface that transparent pressure-sensitive adhesive sheet sticks on nesa coating by nesa coating claimed in claim 5 is fixing.
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| JP2010223530 | 2010-10-01 | ||
| JP2010-223530 | 2010-10-01 | ||
| PCT/JP2011/072054 WO2012043550A1 (en) | 2010-10-01 | 2011-09-27 | Photocurable composition for transparent adhesive sheet |
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| CN103140560B true CN103140560B (en) | 2014-05-28 |
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| JP (1) | JP5701892B2 (en) |
| KR (1) | KR101442442B1 (en) |
| CN (1) | CN103140560B (en) |
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| WO2013088889A1 (en) * | 2011-12-13 | 2013-06-20 | 昭和電工株式会社 | Production method for transparent double-sided adhesive sheet, and transparent double-sided adhesive sheet |
| JP5989381B2 (en) * | 2012-04-05 | 2016-09-07 | スリーエム イノベイティブ プロパティズ カンパニー | Radiation curable adhesive composition and laminate using the same |
| KR101722004B1 (en) * | 2012-10-31 | 2017-03-31 | 쇼와 덴코 가부시키가이샤 | Polymerizable composition, polymer, optical adhesive sheet, image display device and production method for same |
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| TWI512075B (en) | 2015-12-11 |
| CN103140560A (en) | 2013-06-05 |
| WO2012043550A1 (en) | 2012-04-05 |
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| JPWO2012043550A1 (en) | 2014-02-24 |
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